Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Definitions

• the present invention relates to a process for producing polyethylene having impact resistance and to a catalyst for use in such a process.
• Polyethylene is known for use in the manufacture of a wide variety of articles.
• the polyethylene polymerization process can be varied in a number of respects to produce a wide variety of resultant polyethylene resins having different physical properties which render the various resins suitable for use in different applications.
• polyethylene for use in applications where the polyethylene is required to have impact resistance.
• polyethylene is known for use in the manufacture of pipes where it is obviously required that the material of the pipe has sufficient impact resistance so as to avoid inadvertent fracture in service.
• polyethylene is known for use as a film where the property of impact resistance of the film can be of importance.
• Chromium-based catalysts used for the production of polyethylene have been known for some time.
• the catalysts may have been subjected to pre-treatment processes prior to the polymerization reaction.
• the pre-treatment processes may include chemical reduction of the chromium to a lower valence state, e.g. by carbon monoxide. Such a process is disclosed in, for example, EP-A-0591968.
• U.S. Pat. No. 5,208,309 discloses a linear, very low density polyethylene polymerization process.
• a cocatalyst such as a boron alkyl, most particularly triethyl borane (TEB) which tends to generate an in situ comonomer and thus depresses the density of the resultant polyethylene resin.
• the catalyst support is a silica-titania support and for producing a polymer with the most desirable characteristics it is preferred for the support to contain 5 to 8 wt % titanium. The specification does not address the problem of the production of polyethylene having impact resistance.
• U.S. Pat. No. 4,151,122 discloses the reduction and reoxidation of a cogel or self-reduced catalyst in which oxidation of a catalyst is employed after reduction of a catalyst, such as by carbon monoxide, for boosting the melt index of the resultant polyethylene resin. There is no disclosure of a process for producing polyethylene having impact resistance.
• U.S. Pat. No. 4,405,768 discloses the addition of titanium to a catalyst for boosting the melt index of the polyethylene resin. Again, there is no disclosure of a process for producing polyethylene having impact resistance.
• EP-A-0000751 and its equivalent U.S. Pat. No. 4,180,481 disclose a process for the manufacture of a supported chromium oxide catalyst for olefin polymerization, the catalyst having been treated with carbon monoxide. There is no disclosure of a process for producing polyethylene having impact resistance.
• the present invention aims in one aspect to provide a process for producing polyethylene having improved impact resistance.
• the physical properties, in particular the mechanical properties, of a polyethylene product vary depending on what catalytic system was employed to make the polyethylene. This is because different catalyst systems tend to yield different molecular weight distributions in the polyethylene produced.
• the properties of a polyethylene product produced using a chromium-based catalyst i.e. a catalyst known in the art as an “Phillips catalyst”
• a chromium-based catalyst tend to be different from the properties of a polyethylene produced using a different catalyst, for example a Ziegler-Natta catalyst.
• the production of polyethylene using a chromium-based catalyst is desirable to enable the particular polyethylene product obtainable thereby to be manufactured.
• the present invention aims to provide a process for producing polyethylene having impact resistance using a chromium-based catalyst.
• the present invention provides a process for producing polyethylene having impact resistance, the process comprising polymerizing ethylene, or copolymerizing ethylene and an alpha-olefinic comonomer comprising from 3 to 10 carbon atoms, in the presence of a chemically reduced chromium-based catalyst containing in a support thereof from 2 to 3 wt % of titanium, based on the weight of the catalyst.
• the present invention further provides a chromium-based catalyst for the production of polyethylene by polymerizing ethylene or copolymerizing ethylene and an alpha-olefinic comonomer comprising from 3 to 10 carbon atoms, the catalyst being chemically reduced and containing in a support from 2 to 3 wt % of titanium, based on the weight of the catalyst.
• the present invention is predicated on the surprising discovery by the present inventor that the chemical reduction, preferably by carbon monoxide, of a chromium-based catalyst containing from 2 to 3 wt % titanium in its support can unexpectedly yield a polyethylene product having improved impact resistance.
• the chromium-based catalyst preferably comprises a supported chromium oxide catalyst having a titania-containing support, for example a composite silica and titania support.
• a particularly preferred chromium-based catalyst may comprise from 0.5 to 5 wt % chromium, preferably around 1 wt % chromium, such as 0.9 wt % chromium based on the weight of the chromium-containing catalyst.
• the support comprises 2 to 3 wt % titanium, more preferably around 2.3 wt % titanium, based on the weight of the chromium containing catalyst.
• the chromium-based catalyst may have a specific surface area of from 200 to 700 m 2 /g, preferably from 400 to 550 m 2 /g and a volume porosity of greater than 2 cc/g preferably from 2 to 3 cc/g.
• a particularly preferred chromium-based catalyst for use in the present invention comprises a catalyst, (“catalyst 1”) having an average pore radius of 190 ⁇ , a pore volume of around 2.1 cc/g, a specific surface area of around 510 m 2 /g and a chromium content of around 0.9 wt % based on the weight of the chromium-containing catalyst.
• the support comprises a composite silica and titania support. The amount of titania in the support provides that the catalyst as a whole comprises around 2.3 wt % titanium.
• the catalyst may be subjected to an initial activation step in air at an elevated activation temperature.
• the activation temperature preferably ranges from 500 to 850° C., more preferably 600 to 750° C., and is most particularly around 635° C.
• the chromium-based catalyst is subjected to a chemical reduction process in which at least a portion of the chromium is reduced to a low valance state.
• the chromium-based catalyst is reduced in an atmosphere of dry carbon monoxide at a temperature of from 250 to 500° C., more preferably 350 to 450° C., and most preferably at a temperature of around 370° C.
• the polymerization or copolymerization process is carried out in the liquid phase, the liquid comprising ethylene, and where required an alpha-olefinic comonomer comprising from 3 to 10 carbon atoms, in an inert diluent.
• the comonomer may be selected from 1-butene, 1-pentene, 1-hexene, 4-methyl 1-pentene, 1-heptene and 1-octene.
• the inert diluent is preferably isobutane.
• the polymerization or copolymerization process is typically carried out at a temperature of from 90 to 100° C., more preferably from 95 to 100° C., and at a pressure of 20 to 42 bars, more preferably at a minimum pressure of around 24 bars.
• the ethylene monomer comprises from 0.5 to 8% by weight, typically around 6% by weight, of the total weight of the ethylene in the inert diluent.
• the ethylene monomer comprises from 0.5 to 6% by weight and the comonomer comprises from 0.5 to 3% by weight, each based on the total weight of the ethylene monomer and comonomer in the inert diluent.
• the carbon monoxide-reduced catalyst for use in the process of the invention is introduced into the polymerization reactor.
• the alkylene monomer, and comonomer if present, are fed into the polymerization reactor in the inert diluent and the polymerization product of polyethylene is discharged from the reactor and separated from the diluent which can then be recycled.
• the process in order to achieve good impact resistance for the polyethylene, is performed in order to achieve high density in the polyethylene. Accordingly, the process is carried out in the absence of a cocatalyst such as triethyl borane (TEB) which would tend to depress the density, and thus lower the impact resistance.
• TEB triethyl borane
• the polyethylene has a density of from 0.940 to 0.950 g/cc and a high load melt index (HLMI) for resins within that density range of from 5 to 12 g/10 min.
• the polyethylene resin has a shear response (SR) of less than 80.
• the process of the present invention can provide polyethylene resins having improved impact resistance.
• the impact resistance of the film as measured by impact of a dart can be significantly improved as compared to the use of an equivalent catalyst which has not been subjected to carbon monoxide reduction.
• the impact resistance of the pipe under pressure can be greatly increased as compared to the impact resistance of an equivalent pipe employing a polyethylene resin prepared by a polymerization process using substantially the same chromium-based catalyst but not subjected to carbon monoxide reduction.
• Example 1 a polyethylene resin was produced by the polymerization process of the present invention in which a carbon monoxide-reduced chromium-based catalyst was employed.
• the catalyst employed in Example 1 was the chromium-based catalyst identified as catalyst 1 above which had been activated in dry air at a temperature of around 635° C. and then subjected to a dry carbon monoxide reduction at a temperature of 370° C.
• the catalyst had a pore volume of 2.1 cc/g and a specific surface area of 510 m 2 /g.
• the catalyst comprised 0.9% Cr and 2.3% Ti, each based on the weight of the catalyst.
• Example 1 a liquid comprising 6.4 wt % ethylene, 0.6 wt % 1-hexene and the balance isobutane as an inert diluent was fed into a polymerization reaction zone at a pressure of 42 bars and at a polymerization temperature of 95° C. The catalyst was also fed into the polymerization reaction zone. The resultant polyethylene resin was separated from the diluent and following processing to form pellets, the physical properties of the resultant resin were measured. These are shown in Table 1.
• the resultant resin had a high load melt index (HLMI) of 8.5 g/10, the high load melt index having been determined using the procedures of ASTM D 1238 using a load of 21.6 kg at a temperature of 190° C.
• the melt index (MI 2 ) was similarly measured (using the same procedures, with a load of 2.16 kg at 190° C.) and the ratio HMLI/MI 2 was calculated to yield a value for the shear response (SR) of the polyethylene resin of Example 1 of 68.
• the density of the polyethylene resin was measured as 0.946 g/cc, as shown in Table 1.
• the polyethylene resin was then formed into a pipe having a diameter of 110 mm.
• the pipe was then subjected to an impact resistance test at 0° C. by subjecting the pipe to internal pressurization. This test known as the RCP 54 test, was in accordance with ISO/DIS 13477 or EN33477. It will be seen from Table 1 that the pipe failed at an internal pressurization of greater than 12 bars.
• the polyethylene resin was also formed into a 10 micron and a 20 micron thick film, each of which was then subjected to impact by a weighted dart. This test was in accordance with ASTM 1709 Method A. It will be seen from Table 1 that the 10 micron film was penetrated by a dart having a weight of 131 grams and that the 20 micron film was penetrated by a dart having a weight of 155 grams.
• Table 1 also shows equivalent processing parameters and properties of the resin, pipe and film of the polyethylene resin produced in accordance with Comparative Example 1 in which the same chromium-based catalyst as in Example 1 was employed in the production of a polyethylene resin, but with the catalyst having not been subjected to a carbon monoxide reduction.
• Table 1 further shows equivalent processing parameters and properties of the resin and film of the polyethylene resin produced in accordance with Comparative Example 2 in which the catalyst employed was a carbon monoxide-reduced chromium-based catalyst having a low titanium content in the support.
• the catalyst employed was a catalyst, identified as “catalyst 2” having a pore volume of 2.1 cc/g and a specific surface area of 420 m 2 /g.
• the catalyst contained 0.9% Cr but only 1.45% Ti, each based on the weight of the catalyst.
• the catalyst, as for Example 1 was activated at around 635° C. and then subjected to a dry carbon monoxide reduction at a temperature of 370° C.
• Example 1 The resultant polyethylene was, as for Example 1, formed into 10 micron and 20 micron films and subjected to the same impact tests as for Example 1. It will be seen from Table 1 that the films of Comparative Example 2 had significantly lower film impact resistance than those of Example 1, the 10 and 20 micron films being penetrated by darts of less than 30 g and 47 g respectively.
• the results of Example 1 and Comparative Example 2 show that the use, in conjunction with carbon monoxide reduction, of a catalyst support having a titanium content of at least 2% provides improved impact resistance to the polyethylene.
• a different catalyst was employed having the properties specified in Table 1.
• the catalyst was subjected to zero reduction and activation similar to those for Comparative Example 2 but using the temperatures specified in Table 1.
• the resultant resin had the properties HLMI, shear response and density as specified in Table 1.
• a film produced from the resultant resin was tested for impact resistance as for the previous Comparative Examples and the results are shown in Table 1. It may be seen that the use of a catalyst having a titanium content of 5% by weight, i.e. greater than the 3% limit required by the present invention, yields reduced impact resistance as compared to the present invention.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Graft Or Block Polymers (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

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Citations (9)

• 1997
  • 1997-02-07 EP EP97101975A patent/EP0857737A1/fr not_active Withdrawn
• 1998
  • 1998-02-09 JP JP53377898A patent/JP2001510504A/ja active Pending
  • 1998-02-09 US US09/020,936 patent/US6194528B1/en not_active Expired - Fee Related
  • 1998-02-09 EP EP98908075A patent/EP0958310B1/fr not_active Expired - Lifetime
  • 1998-02-09 DE DE69809886T patent/DE69809886T2/de not_active Expired - Fee Related
  • 1998-02-09 ES ES98908075T patent/ES2187008T3/es not_active Expired - Lifetime
  • 1998-02-09 AT AT98908075T patent/ATE229041T1/de not_active IP Right Cessation
  • 1998-02-09 WO PCT/EP1998/000714 patent/WO1998034963A1/fr active IP Right Grant
  • 1998-02-09 PT PT98908075T patent/PT958310E/pt unknown

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